CN101240117B - Pure organic dyestuff and dyestuff sensitization solar energy battery prepared therefrom - Google Patents

Pure organic dyestuff and dyestuff sensitization solar energy battery prepared therefrom Download PDF

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CN101240117B
CN101240117B CN2008100503715A CN200810050371A CN101240117B CN 101240117 B CN101240117 B CN 101240117B CN 2008100503715 A CN2008100503715 A CN 2008100503715A CN 200810050371 A CN200810050371 A CN 200810050371A CN 101240117 B CN101240117 B CN 101240117B
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structural formula
dye
organic dye
pure organic
sensitization solar
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CN101240117A (en
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许名飞
秦浩
高飞飞
王鹏
赛克·扎克鲁丁
迈克尔·格雷泽
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Changzhou Institute Of Energy Storage Materials & Devices
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Changchun Institute of Applied Chemistry of CAS
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Priority to US12/735,629 priority patent/US8487119B2/en
Priority to PCT/IB2009/050441 priority patent/WO2009098643A2/en
Priority to JP2010545587A priority patent/JP5576298B2/en
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Abstract

The invention relates to a pure organic dye the molecular structure of which is D-pi-A and dye-sensitized solar cells prepared therefrom. When the pure organic dye that is the most efficient one in the world serves as a sensibilizer used in dye-sensitized solar cells, a photoelectric transformation efficiency of not less than 99% and a battery efficiency of not less than 10% are obtained, almost reaching the battery efficiency of dye-sensitized solar cells with the aid of precious metals complex dye sensibilizer, so a potential application of the pure organic dye is provided.

Description

Pure organic dye and dye sensitization solar battery prepared therefrom
Technical field
The present invention relates to organic dye and dye sensitization solar battery prepared therefrom.
Background technology
Along with shortage of resources and problem of environmental pollution become increasingly conspicuous, people day by day strengthen the care of energy problem.For thereby the energy of developing alternative traditional fossil oil solves the energy dilemma of approaching day by day, the mankind have carried out various trial researchs.In the alternative energy, the solar cell utilization be that to compare with other energy be to be unlimited and environment amenable sun power basically, carrying out opto-electronic conversion by solar cell is one of main path of human use's sun power.In solar cell, high and technology maturation has occupied the solar cell major portion to silicon solar cell because of its turnover ratio, it is high and having difficulties aspect the battery efficiency improving that but silicon solar cell exists production cost, and the prices of raw and semifnished materials are expensive and be difficult to popularize.
Different with silicon solar cell, dye sensitization solar battery is mainly by absorbing visible light and producing that the transition metal oxide of the light-sensitive coloring agent molecule of electron-hole pair and the electronics that transmission produces constitutes, compare with silicon solar cell, have efficient, low cost, less energy-consumption, advantages of environment protection, demonstrate powerful commercial application prospect.Since making a breakthrough aspect the dye sensitization solar battery research, become the focus (Nature 1991,353,737) of countries in the world research from Switzerland Gratzel professor in 1991 gradually.At present, the best dye sensitizing agent of performance is the organic sensitizing agent of metal that contains precious metal, as many pyridines ruthenium complexe (J.Am.Chem.Soc.2005,127,16835-16847), however because the finiteness of its higher price and precious metal resource has limited its practical application.Compare with many pyridines ruthenium complexe, the pure organic dye that does not contain precious metal has that cost is low, optical extinction coefficient is high and characteristics such as the Adjustable structure control is strong, replaced gradually in recent years contain many pyridines ruthenium complexe and become the focus of this area research (J.Am.Chem.Soc.2006,128,16701-16707).
Summary of the invention
Organic dye has good hole transport performance and strong electron donation, can obtain organic dye sensitized efficiently dose by rational molecular designing, and this improves for the dye sensitization solar battery performance and the cost reduction has crucial meaning.
1) the pure organic dye of a class provided by the invention, it has following chemical structural formula 1:
In the formula, R 1, R 2, R 3, R 4, R 5And R 6Be in hydrogen atom, alkyl, aryl, alkoxyl group or heterocycle and the derivative thereof any one;
R is made up of any one or a plurality of group among the following structural formula 2-21:
Structural formula 2
Figure S2008100503715D00022
Structural formula 3
Figure S2008100503715D00031
Structural formula 4
Structural formula 5
Figure S2008100503715D00033
Structural formula 6
Figure S2008100503715D00034
Structural formula 7
Figure S2008100503715D00035
Structural formula 8
Figure S2008100503715D00041
Structural formula 9
Structural formula 10
Figure S2008100503715D00043
Structural formula 11
Figure S2008100503715D00044
Structural formula 12
Figure S2008100503715D00051
Structural formula 13
Figure S2008100503715D00052
Structural formula 14
Figure S2008100503715D00053
Structural formula 15
Figure S2008100503715D00054
Structural formula 16
Figure S2008100503715D00061
Structural formula 17
Figure S2008100503715D00062
Structural formula 18
Figure S2008100503715D00063
Structural formula 19
Structural formula 20
Figure S2008100503715D00071
Structural formula 21
Figure S2008100503715D00072
In the formula, R 7To R 66In group, alkyl sulphonyl, alkylthio, ester group, alkylhalide group, halogen, alkylsulfonyl, cyano group, alkenyl, acyloxy, carboxyl and the heterocycle of forming for hydrogen atom, hydroxyl, nitro, amino, acyl group, alkyl, cycloalkyl, alkoxyl group, aromatic hydrocarbon and derivative thereof any one;
A is an electron-withdrawing group, and it is in cyano group, acyl group, aldehyde radical, carboxyl, amido, sulfonic group, nitro, haloform base and the quaternary amine base any one;
B is any one in carboxyl, phosphorous acid, sulfonic acid, Hypophosporous Acid, 50, hydroxyl, oxidation carboxylic acid, acid amides, boric acid and the square acid.
2) the invention provides preferred organic dye, its structural formula is I-X:
Structural formula I
Figure S2008100503715D00081
Structural formula II
Structural formula II I
Figure S2008100503715D00083
Structural formula IV
Figure S2008100503715D00091
Structural formula V
Structural formula VI
Figure S2008100503715D00093
Structural formula VII
Figure S2008100503715D00101
Structural formula VIII
Structural formula IX
Figure S2008100503715D00103
Structural formula X
Figure S2008100503715D00111
3) the invention provides dye sensitization solar battery, shown in Fig. 3 and 4, it constitutes it and comprises: transparent substrates layer 1, conductive layer 2, light absorbing zone 3, dielectric substrate 6 and counter electrode 7 constitute; What connect in turn in the middle of 2 transparent substrates layers 1 is conductive layer 2, light absorbing zone 3, dielectric substrate 6 and counter electrode 7; Described light absorbing zone 3 is made of semiconductor nano-particles layers 4 and dye coating 5, and wherein, semiconductor nano-particles layers 4 is connected with conductive layer 2, and dye coating 5 is connected with dielectric substrate 6;
Described transparent substrates layer 1 is that substrate of glass or plastics constitute; Described plastics are wherein any one of polyethylene terephthalate, PEN, polycarbonate, polypropylene, polyimide, tri acetyl cellulose and polyethersulfone;
Described conductive layer 2 is by tin indium oxide (ITO), fluorine oxide tin (FTO), ZnO-Ga 2O 3, ZnO-Al 2O 3, any one formation in tin-based oxide, antimony tin (ATO) and the zinc oxide;
The semi-conductor nano particles of described semiconductor nano-particles layers 4 is Si, TiO 2, SnO 2, ZnO, WO 3, Nb 2O 5And TiSrO 3In any one, the median size≤50nm of 0nm＜semi-conductor nano particles;
The organic dye that described dye coating 5 is a chemical structural formula 1 constitutes;
Described dielectric substrate 6 is iodine/lithium iodide ionogen, perhaps any one formation in ionic liquid and the organic hole transport material;
Positively charged ion is selected from
Figure DEST_PATH_GSB00000076580300011
In any one;
The organic hole transport material is 2,2 ', 7,7 '-four (N, N-di-p-methoxy phenyl amidos) 9,9 '-spiro-bisfluorene;
Described counter electrode 7 is by any one or a plurality of composition the in Pt, Au, Ni, Cu, Ag, In, Ru, Pd, Rh, Ir, Os, C and the conductive polymers;
Described conductive polymers is any one in polyaniline, polypyrrole, Polythiophene, p-phenylene vinylene and the polyethers.
4) preparation method of organic dye of the present invention, its synthetic route is as follows:
Figure DEST_PATH_GSB00000076580300012
Synthesizing of the material of structural formula a:
With R 1I, R 2The para-bromoaniline of I, replacement and toluene with etc. mixed in molar ratio, reaction system places under the Ar gas shiled, be warming up to 120 ℃ of back flow reaction 24 hours, add the water termination reaction, use chloroform extraction after being cooled to room temperature, organic phase washing three times, use anhydrous sodium sulfate drying, remove and desolvate, column chromatography obtains product a; Described R 1, R 2Be in hydrogen atom, alkyl, aryl, alkoxyl group or heterocycle and the derivative thereof any one.
Synthesizing of the material of structural formula b:
Material, four-triphenyl phosphorus palladium, solution of potassium carbonate and the RB (OH) of the structural formula a that back is obtained 2Or RSnBu 3With mol ratio 1: 1: 0.8: 0.1; be dissolved in material a mol ratio be in 1: 500 the tetrahydrofuran (THF); reaction system places under the Ar gas shiled; be warming up to 70 ℃ of reactions 24 hours, system is cooled to the room temperature after-filtration, and organic phase is used sodium carbonate solution and washed three times; use anhydrous sodium sulfate drying; remove and desolvate, column chromatography obtains product b.
Synthesizing of the material of structural formula c:
Material, the anhydrous N of the structural formula b that back is obtained; N '-dimethyl formamide (DMF) and 1; the 2-ethylene dichloride mixes with mol ratio at 1: 10: 400; under protection of inert gas, drip after being cooled to 0 ℃ with material b mol ratio be 1: 1.2 times of phosphorus oxychloride, be warming up to 84 ℃ of back flow reaction 4 hours.Add the water termination reaction, with sodium acetate neutralization, chloroform extraction, the organic phase drying is removed and is desolvated, and column chromatography obtains product c.
Synthesizing of the organic dye of structural formula 1:
Material, the ACH of the structural formula c that back is obtained 2B, piperidines and acetonitrile were with mol ratio 1: 1.1: 10: 600 mix; reaction system places under the Ar gas shiled; be warming up to 6 hours postcooling of 82 ℃ of back flow reaction, acetonitrile is steamed, add water; transfer pH to 1～2 with hydrochloric acid; use dichloromethane extraction, the organic phase drying is removed and is desolvated; column chromatography obtains the organic dye of structural formula 1.
5) method for preparing dye sensitization solar battery of the organic dye by structural formula 1 provided by the invention, its step and condition are as follows:
Preparation TiO 2Nanocrystalline and TiO 2The preparation of nanostructure duplicature electrode; Adopt method (reference Wang P.et al., the Enhance thePerformance of Dye-Sensitized Solar Cells by Co-grafting AmphiphilicSensitizer and Hexadecylmalonic Acid on TiO of following reference 2Nanocrystals, J.Phys.Chem.B., 107,2003,14336);
With the TiO for preparing 2Nanostructure duplicature electrode is immersed in dyestuff and the 10mMCheno (3 that contains 300 μ M structural formulas 1,7-dihydroxyl-4-cholic acid) in the chlorobenzene, time is 12 hours, at this moment, dye molecule just is adsorbed on the electrode, and can guarantee fraction of coverage more than 90%, then the glass electrode of nanometer platinum is melted the same TiO of ring by one the 35 thick heat of μ m 2Nanostructure duplicature heated by electrodes is melting sealed, at last electrolyte is injected in the slit of two electrodes, has promptly constituted dye sensitization solar battery.Detailed preparation method is referring to document (Wang P.et al., A Solvent-Free, SeCN -/ (SeCN) 3 -Based IonicLiquid Electrolyte for High-Efficiency Dye-Sensitized NanocrystallineSolar Cell, J.Am.Chem.Soc., 126,2004,7164).
Beneficial effect of the present invention:
Organic dye provided by the invention is used for dye sensitization solar battery as sensitizing agent, has obtained the photoelectric transformation efficiency more than 90% and has been higher than 10% battery efficiency (seeing specification sheets subordinate list and accompanying drawing).Be used for dye sensitization solar battery as sensitizing agent, this is an organic dye the most efficiently in the world so far, near using the efficient of the dye sensitization solar battery of precious metals complex dye sensitizing agent, has a good application prospect.
Description of drawings
Fig. 1 is provided by the invention by the photoelectric transformation efficiency of dye-sensitized solar cell prepared shown in the structural formula 1 and the graphic representation of wavelength.
Fig. 2 is provided by the invention by dye-sensitized solar cell prepared electric current shown in the structural formula 1 and voltage curve figure.
Fig. 3 is the structural representation by the dye sensitization solar battery of organic dye preparation.This figure also is a Figure of abstract.
Fig. 4 is light absorbing zone 3 structural representations.Among the figure, 4 is semiconductor nano-particles layers, and 5 is dye coating.
Embodiment
Embodiment 1:
The synthetic route of the organic dye of structural formula I is as follows:
Figure S2008100503715D00161
Structural formula is material synthetic of a:
Take by weighing 0.256g (0.46mmol) 2-[N; N-two (9; 9-dimethyl fluorene-2-yl) phenyl]-bromine; 0.1g (0.51mmol) two thiophthene boric acid; 0.058g (0.051mmol) four-triphenyl phosphorus palladium; 1.7 milliliter 2mol/L solution of potassium carbonate and 17 milliliters of tetrahydrofuran (THF)s join in 50 milliliters of round-bottomed flasks, reaction system places under the argon shield, is warming up to 70 ℃ of reactions 24 hours.System is cooled to the room temperature after-filtration, chloroform extraction, and organic phase is used sodium carbonate solution and is washed three times.The organic phase anhydrous sodium sulfate drying removes and desolvates.Column chromatography (developping agent toluene: normal hexane volume ratio 1: 5), obtain faint yellow solid product a, productive rate 86%.
Structural formula is material synthetic of b:
The material a0.286g (0.465mmol) that back is obtained is dissolved in milliliter 1; the 2-ethylene dichloride; add 0.36 milliliter of anhydrous N; N '-dimethyl formamide (DMF); after being cooled to 0 ℃ under protection of inert gas Dropwise 5 1.1 μ L (0.558mmol) phosphorus oxychloride, be heated to 84 ℃ of back flow reaction 4 hours.Add the water termination reaction, with sodium acetate neutralization, chloroform extraction, the organic phase drying is removed and is desolvated.Column chromatography (developping agent toluene: normal hexane volume ratio 3: 1), obtain orange red solid product b, productive rate 92%.
Synthesizing of the organic dye of structural formula 1:
With the material b0.33g (0.573mmol) that back obtains, 0.053g (0.624mmol) cyanoacetic acid, 20 milliliters of acetonitriles and 0.026 milliliter of piperidines join in 50 milliliters of round-bottomed flasks; reaction system places under the Ar gas shiled; be heated to 6 hours postcooling of 82 ℃ of back flow reaction to room temperature, acetonitrile is removed, add water; transfer pH to 1～2 with hydrochloric acid; use dichloromethane extraction, the organic phase drying is removed and is desolvated; column chromatography (developping agent chloroform) obtains the organic dye of structural formula I.Productive rate 93%.
Embodiment 2: by the dye sensitization solar battery of the organic dye of structural formula I preparation
With granularity is the TiO of 20nm 2Colloid is coated on the adulterated SnO of fluorine 2On the conductive glass, form nano-TiO 2Epitaxial 400 ℃ of following roastings 12 hours, obtains the TiO that thickness is 7 μ m 2Epitaxial; This TiO that is obtaining 2Using same quadrat method on the tunic, is 400nm TiO with granularity 2, roasting thickness is the TiO of 5 μ m 2Light-diffusing films; Obtain TiO 2Nanostructure duplicature electrode.Concrete preparation TiO 2Nanocrystalline and TiO 2The method of nanostructure duplicature electrode is referring to article (Wang P.et al., Enhance the Performance of Dye-Sensitized Solar Cellsby Co-grafting Amphiphilic Sensitizer and Hexadecylmalonic Acid onTiO 2Nanocrystals, J.Phys.Chem.B., 107,2003,14336).
With the TiO for preparing 2Nanostructure duplicature electrode is immersed in the dyestuff and the 10mMCheno (3 of the structural formula 1 that contains 300 μ M, 7-dihydroxyl-4-cholic acid) in the chlorobenzene, time is 12 hours, at this moment, dye molecule just is adsorbed on the electrode, and can guarantee fraction of coverage more than 90%, then the glass electrode of nanometer platinum is melted the same TiO of ring by one the 35 thick heat of μ m 2Nanostructure duplicature heated by electrodes is melting sealed; At last electrolyte is injected in the slit of two electrodes, has promptly constituted dye sensitization solar battery.Detailed device preparation method is referring to document (Wang P.et al., A Solvent-Free, SeCN -/ (SeCN) 3 -Based IonicLiquid Electrolyte for High-Efficiency Dye-Sensitized NanocrystallineSolar Cell, J.Am.Chem.Soc., 126,2004,7164).
Device is measured light intensity 100mw/cm under standard A M1.5 simulated solar irradiation 2, short-circuit photocurrent J ScBe 13.35mA/cm 2, open circuit photovoltage V OcBe 776.6mV, packing factor ff is 0.749, and photoelectric transformation efficiency is 7.8%.
Embodiment 3: the preparation of the organic dye shown in the structural formula II reaches the dye sensitization solar battery by the organic dye preparation of structural formula II
Figure S2008100503715D00191
Just change two thiophthenes among the embodiment 1 into three thiophthenes, synthesize the dyestuff that structural formula is II according to step and the condition of embodiment 1; Method according to embodiment 2 prepares dye sensitization solar battery, just is that the organic dye of I changes the organic dye shown in the structural formula II into structural formula.The dye sensitization solar battery parameter that obtains is seen the specification sheets subordinate list.
Embodiment 4: the preparation of the organic dye shown in the structural formula II I reaches the dye sensitization solar battery by the organic dye preparation of structural formula II I
Figure S2008100503715D00192
Just change two thiophthenes among the embodiment 1 into the thiophene fluorenes, synthesize the dyestuff that structural formula is III according to step and the condition of embodiment 1; Method according to embodiment 2 prepares dye sensitization solar battery, just is that the organic dye of I changes the organic dye shown in the structural formula II I into structural formula.The dye sensitization solar battery parameter that obtains is seen the specification sheets subordinate list.
Embodiment 5: the preparation of the organic dye shown in the structural formula IV reaches the dye sensitization solar battery by the organic dye preparation of structural formula IV
Synthetic route is as follows:
Figure S2008100503715D00201
Structural formula is material synthetic of c
With 0.7g (1.62mmol) tributyl tin ethene dioxythiophene and 0.6g (1.08mmol) 2-[N; N-two (9; 9-dimethyl fluorene-2-yl) phenyl]-bromine is dissolved in 45 milliliters of toluene; add 0.084g (0.119mmol) two-triphenyl phosphorus palladium chloride and 0.14g (0.119mmol) four-triphenyl phosphorus palladium; under argon shield, be warming up to 115 ℃ of back flow reaction.Add the water termination reaction, with toluene extraction, the organic phase drying, remove and desolvate behind the cool to room temperature, column chromatography obtains the material that structural formula is c.
Structural formula is material synthetic of d
The material c0.25g (0.405mmol) that back is obtained is dissolved in 20 milliliter 1, in the 2-ethylene dichloride, adds 0.32 milliliter of (4.05mmol) DMF, solution is cooled to 0 ℃, add 0.045 milliliter of (0.486mmol) phosphorus oxychloride, 0 ℃ was reacted 1 hour, rose to room temperature reaction 5 hours.Add 20 milliliters of sodium acetate solutions, stirring at room 30 minutes, dichloromethane extraction, the organic phase drying is removed and is desolvated, and obtains the material that structural formula is d.
Structural formula is dyestuff synthetic of IV
The material d0.28g (0.43mmol) that back is obtained is dissolved in 60 milliliters of acetonitriles, adds 0.02 milliliter of (0.22mmol) piperidines and 0.044g (0.52mmol) cyanoacetic acid, is warming up to 82 ℃ of back flow reaction 24 hours under argon shield.Add the water termination reaction, with hydrochloric acid adjust pH to 1～2, dichloromethane extraction, the organic phase drying is removed and is desolvated silica gel column chromatography (developping agent: chloroform), obtain the dyestuff that structural formula is IV.
Method according to embodiment 2 prepares dye sensitization solar battery, just is that the organic dye of I changes the dyestuff that structural formula is IV into structural formula.(battery parameter is seen the specification sheets subordinate list)
Embodiment 6: the preparation of the pure organic dye shown in the structural formula V reaches the dye sensitization solar battery by the pure organic dye preparation of structural formula V
Figure S2008100503715D00211
Just change the ethene dioxythiophene among the embodiment 5 into the di-thiophthene, synthesize the dyestuff that structural formula is V according to step and the condition of embodiment 5; Method according to embodiment 2 prepares dye sensitization solar battery, just is that the pure organic dye of I changes the pure organic dye shown in the structural formula V into structural formula.The dye sensitization solar battery parameter that obtains is seen the specification sheets subordinate list.
Embodiment 7: the preparation of the pure organic dye shown in the structural formula VI reaches the dye sensitization solar battery by the pure organic dye preparation of structural formula VI
Figure S2008100503715D00221
Just the ethene dioxythiophene among the embodiment 5 is changed into di-and three thiophthenes, synthesize the dyestuff that structural formula is VI according to step and the condition of embodiment 5; Method according to embodiment 2 prepares dye sensitization solar battery, just is that the pure organic dye of I changes the pure organic dye shown in the structural formula VI into structural formula.The dye sensitization solar battery parameter that obtains is seen the specification sheets subordinate list.
Embodiment 8: the preparation of the pure organic dye shown in the structural formula VII reaches the dye sensitization solar battery by the pure organic dye preparation of structural formula VII
Figure S2008100503715D00222
Just change the ethene dioxythiophene among the embodiment 5 into divinyl dioxy thiophene-ethylene dioxy two thiophthenes, synthesize the dyestuff that structural formula is VII according to step and the condition of embodiment 5; Method according to embodiment 2 prepares dye sensitization solar battery, just is that the pure organic dye of I changes the pure organic dye shown in the structural formula VII into structural formula.The dye sensitization solar battery parameter that obtains is seen the specification sheets subordinate list.
Embodiment 9: the preparation of the pure organic dye shown in the structural formula VIII reaches the dye sensitization solar battery by the pure organic dye preparation of structural formula VIII
Figure S2008100503715D00231
Just change the ethene dioxythiophene among the embodiment 5 into divinyl dioxy thiophene-thiophene fluorenes, synthesize the dyestuff that structural formula is VIII according to step and the condition of embodiment 5; Method according to embodiment 2 prepares dye sensitization solar battery, just is that the pure organic dye of I changes the pure organic dye shown in the structural formula VIII into structural formula.The dye sensitization solar battery parameter that obtains is seen the specification sheets subordinate list.
Embodiment 10: the preparation of the pure organic dye shown in the structural formula IX reaches the dye sensitization solar battery by the pure organic dye preparation of structural formula IX
Figure S2008100503715D00232
Just change the ethene dioxythiophene among the embodiment 5 into divinyl dioxy thiophene-two thiophthenes-ethene dioxythiophene, synthesize the dyestuff that structural formula is IX according to step and the condition of embodiment 5; Method according to embodiment 2 prepares dye sensitization solar battery, just is that the pure organic dye of I changes the pure organic dye shown in the structural formula IX into structural formula.The dye sensitization solar battery parameter that obtains is seen the specification sheets subordinate list.
Embodiment 11: the preparation of the pure organic dye shown in the structural formula X reaches the dye sensitization solar battery by the pure organic dye preparation of structural formula X
Figure S2008100503715D00241
Just change the ethene dioxythiophene among the embodiment 5 into divinyl dioxy thiophene-two thiophthene-three thiophthene, synthesize the dyestuff that structural formula is X according to step and the condition of embodiment 5; Method according to embodiment 2 prepares dye sensitization solar battery, just is that the pure organic dye of I changes the pure organic dye shown in the structural formula X into structural formula.The dye sensitization solar battery parameter that obtains is seen the specification sheets subordinate list.
Subordinate list: by the standard element of the dye-sensitized solar cell prepared of structural formula I-X
The parameter measurements table
The dye structure formula Open circuit voltage (mV) Short-circuit current (mA/cm 2) Packing factor ff Efficient (%)
I 776.6 13.35 0.749 7.8
II 778.2 13.98 0.726 8.4
III 773.6 12.66 0.784 8.0
IV 780.3 14.65 0.731 8.5
V 772.1 15.93 0.719 9.6
VI 782.9 14.84 0.734 8.7
VII 777.9 14.55 0.744 8.8
VIII 774.7 16.70 0.711 9.9
IX 765.2 16.54 0.738 9.7
X 779.8 16.78 0.712 10.2

Claims (2)

1. pure organic dye is characterized in that, it is structural formula I-X any one:
Structural formula I
Figure FSB00000076580400011
Structural formula II
Figure FSB00000076580400012
Structural formula II I
Figure FSB00000076580400021
Structural formula IV
Figure FSB00000076580400022
Structural formula V
Figure FSB00000076580400031
Structural formula VI
Figure FSB00000076580400032
Structural formula VII
Figure FSB00000076580400033
Structural formula VIII
Figure FSB00000076580400041
Structural formula IX
Figure FSB00000076580400042
Structural formula X
Figure FSB00000076580400043
2. with the dye sensitization solar battery of the described pure organic dye preparation of claim 1, it is characterized in that its formation comprises: transparent substrates layer (1), conductive layer (2), light absorbing zone (3), dielectric substrate (6) and counter electrode (7) constitute; What connect in turn in the middle of 2 transparent substrates layers (1) is conductive layer (2), light absorbing zone (3), dielectric substrate (6) and counter electrode (7); Described light absorbing zone (3) is made of semiconductor nano-particles layers (4) and dye coating (5), and wherein, semiconductor nano-particles layers (4) is connected with conductive layer (2), and dye coating (5) is connected with dielectric substrate (6);
Described transparent substrates layer (1) is that substrate of glass or plastics constitute; Described plastics are wherein any one of polyethylene terephthalate, PEN, polycarbonate, polypropylene, polyimide, tri acetyl cellulose and polyethersulfone;
Described conductive layer (2) is by tin indium oxide, ZnO-Ga 2O 3, ZnO-Al 2O 3, any one formation in tin-based oxide, antimony tin and the zinc oxide;
The semi-conductor nano particles of described semiconductor nano-particles layers (4) is Si, TiO 2, SnO 2, ZnO, WO 3, Nb 2O 5And TiSrO 3In any one, the median size≤50nm of 0nm＜semi-conductor nano particles;
Described dye coating (5) is that the pure organic dye of structural formula I-X constitutes;
Described dielectric substrate (6) is iodine/lithium iodide ionogen, perhaps any one formation in the organic hole transport material;
The organic hole transport material is 2,2 ', 7,7 '-four (N, N-di-p-methoxy phenyl aminos) 9,9 '-spiro-bisfluorene;
Described counter electrode (7) is by any one or a plurality of composition the in Pt, Au, Ni, Cu, Ag, In, Ru, Pd, Rh, Ir, Os, C and the conductive polymers;
Described conductive polymers is any one in polyaniline, polypyrrole, Polythiophene, p-phenylene vinylene and the polyethers.
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